[go: up one dir, main page]

WO2019027152A1 - Procédé de fabrication d'anode de batterie secondaire et anode de batterie secondaire - Google Patents

Procédé de fabrication d'anode de batterie secondaire et anode de batterie secondaire Download PDF

Info

Publication number
WO2019027152A1
WO2019027152A1 PCT/KR2018/007789 KR2018007789W WO2019027152A1 WO 2019027152 A1 WO2019027152 A1 WO 2019027152A1 KR 2018007789 W KR2018007789 W KR 2018007789W WO 2019027152 A1 WO2019027152 A1 WO 2019027152A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium metal
negative electrode
secondary battery
anode
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/007789
Other languages
English (en)
Korean (ko)
Inventor
김주리
김인철
송주용
김석구
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN202311538900.7A priority Critical patent/CN117691050A/zh
Priority to CN201880003741.1A priority patent/CN109792046A/zh
Priority to EP18841091.4A priority patent/EP3503266A4/fr
Publication of WO2019027152A1 publication Critical patent/WO2019027152A1/fr
Priority to US16/376,439 priority patent/US11658285B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for manufacturing a secondary battery anode having improved overall lithium ionization rate of a cathode and a secondary battery anode made by such a method. More particularly, the present invention relates to a lithium battery having a lithium metal deposited on a silicon- In order to increase the releasability between the releasing film and the lithium metal, a releasing film coated with silicon is applied to the negative electrode, and a patterned lithium metal is laminated on the negative electrode to improve the total lithization speed And a secondary battery in which charging is initiated by injecting an electrolyte into the electrode assembly including the negative electrode.
  • a prismatic secondary battery and a pouch-type secondary battery that can be applied to products such as mobile phones with a small thickness.
  • lithium ion batteries having high energy density, discharge voltage
  • a lithium secondary battery such as a lithium ion polymer battery.
  • a secondary battery has a structure in which an active material is applied to the surface of a collector to form an anode and a cathode, an electrode assembly is formed therebetween with a separator interposed therebetween, and then a cylindrical or square metal can or aluminum laminate sheet A liquid electrolyte is injected or impregnated into the electrode assembly, or a solid electrolyte is used.
  • a carbon material such as graphite is used as a negative electrode of a lithium secondary battery, but the theoretical capacity density of carbon is 372 mAh / g (833 mAh / cm3). Therefore, silicon (Si), tin (Sn), oxides thereof and alloys thereof, which are alloyed with lithium to improve the energy density of a cathode, are studied as cathode materials. Among them, silicon-based materials have attracted attention due to their low cost and high capacity (4200 mAh / g).
  • the irreversible capacity is a capacity lost in the first charge / discharge cycle. That is, in the charge / discharge reaction of the conventional secondary battery, lithium discharged from the positive electrode is stored in the negative electrode during charging, and lithium discharged from the negative electrode is stored in the positive electrode during discharging. Therefore, when the irreversible capacity at the cathode is large at the initial charge / discharge, a portion of the reversible capacity originally possessed by the cathode and the anode is lost, so that the battery capacity can not be obtained.
  • the irreversible capacity of the negative electrode is a residue of reversible lithium due to partial deactivation of lithium or hysteresis of the lithium occlusion / discharge potential due to a side reaction with the electrolyte occurring at the time of charging, Is considered to be the cause of the decrease.
  • Korean Patent Registration No. 1162794 discloses a method of manufacturing a negative electrode in which a lithium metal is deposited on a carrier substrate by a vapor phase method and then the deposited lithium metal is occluded in a negative electrode active material layer.
  • this method has a disadvantage in that the manufacturing process is complicated.
  • the present invention provides a lithium secondary battery, A method for manufacturing a negative electrode for uniformly depositing lithium metal on a mixed phase is provided.
  • Another object of the present invention is to provide a method of manufacturing an anode for improving the rate of total lithium ionization of a cathode.
  • the present invention provides a method of manufacturing a lithium metal sheet, comprising the steps of: preparing a lithium metal sheet coated with a lithium metal on a release film and wound in a roll; A second step of laminating the lithium metal sheet so that the lithium metal is adjacent to the negative electrode material mixture to produce a lithium metal laminated anode; And a third step of applying a pressure to a cathode in which lithium metal is stacked to produce a cathode; And the release film is coated with silicon.
  • the present invention also relates to a negative electrode manufactured by any one of the above methods, and a secondary battery including the negative electrode.
  • the lithium metal may have a stripe, mesh, wave, or circular pattern.
  • the lithium metal having a stripe pattern can be produced by cutting lithium metal as a base material into a thin width.
  • the thickness of the lithium metal may be 2 to 200 [mu] m.
  • a method of applying a pressure to a cathode in which lithium metal is stacked can be performed by passing through a pair of rollers or plates.
  • the temperature when passing through the roller or the plate may be 5 to 100 ° C.
  • the pressure when passing through the roller or the plate may be 10 to 100 kg / cm 2.
  • the thickness of the release film may be 5 to 50 mu m.
  • the negative electrode material mixture may be prepared by applying an anode slurry containing silicon oxide on a current collector, followed by drying and rolling.
  • a method of manufacturing an electrode assembly comprising: preparing an electrode assembly between a cathode and an anode; Injecting an electrolyte solution into the electrode assembly; And an aging step, wherein initial charging is initiated by injecting an electrolytic solution.
  • the aging may be performed for 12 to 72 hours.
  • the present invention is a secondary battery in which initial charging is initiated by injecting an electrolyte into an electrode assembly including a cathode manufactured by the above method and a cathode manufactured by the above method.
  • the manufacturing method of the present invention has the effect of uniformly laminating or bonding the lithium metal, which is difficult to handle, to the secondary battery negative electrode mixture.
  • the present invention also has the advantage of improving the rate of total lithization by using a patterned lithium metal.
  • the secondary battery anode manufactured by the method of the present invention has improved initial irreversibility, and the secondary battery manufactured using such a secondary battery anode has excellent charge / discharge efficiency.
  • a negative electrode for a secondary battery comprises: a first step of preparing a lithium metal sheet coated with a lithium metal in the form of a thin film on a release film and wound in a roll; A second step of laminating the lithium metal sheet so that the lithium metal is adjacent to the negative electrode material mixture to produce a lithium metal laminated anode; And a third step of applying a pressure to a cathode in which lithium metal is stacked to produce a cathode; And the release film is characterized in that it is coated with silicon.
  • the silicon oxide cathode is a cathode using silicon and oxides thereof as a main material in order to increase the capacity density of a cathode using a carbon material such as graphite. And has a theoretical capacity density of 4200 mAh / g, which is much higher than the theoretical capacity density of carbon material of 372 mAh / g, and thus can be suitably used as a negative electrode for a secondary battery.
  • silicon oxide cathodes require a pre-lithiation process because of their low form stability and high initial irreversible capacity, which may lead to reduced electrode capacity or destruction of cell balance.
  • Lithium ionization can be accomplished by passing lithium metal through the upper and lower rollers and plates together with the cathode, and by wetting the cathode and lithium metal together in the electrolyte to store the lithium into the cathode.
  • the lithium metal is inherently ductile in nature of its material and is not easy to handle due to its nature of sticking to different materials.
  • a lithium metal sheet coated with a lithium metal on a substrate such as a release or release film can be used. After the lithium metal sheet is bonded to the negative electrode mixture, a part of the lithium metal Is dropped together with the substrate. This is a factor for attenuating the efficiency of total lithization due to the unevenness of the cathode. Therefore, the inventors of the present invention have studied the method in which the lithium metal does not come off together with the base material when the base material is removed.
  • the present invention relates to a method of coating a lithium metal on a silicon-coated substrate and facilitating handling of the lithium metal by using a roll-wound type lithium metal sheet.
  • the substrate is peeled off, So that the lithium metal can be uniformly bonded to the cathode.
  • the present invention is characterized in that, in order to improve the total lithization efficiency, a patterned lithium metal is applied so that the electrolytic solution can be better permeated to the cathode, thereby improving the speed of pre-lithization. This is because, if there is a pattern in the lithium metal bonded to the cathode, the speed of pre-lithization is improved because the movement of lithium ions is faster.
  • the shape of the pattern may be in the form of a stripe, a mesh, a wave, a circle, or a lattice structure.
  • the method of forming the pattern on the lithium metal is not particularly limited, and a known method can be used. Specifically, a lithium metal sheet having a stripe pattern can be obtained by laminating a lithium metal thin film serving as a base material on a release film and then cutting the lithium metal to a thin width. The lithium metal sheet of the mesh pattern, The pattern can be obtained by using a tool having a mesh pattern such as a punching machine. It is also possible to form the pattern using rollers having the form of stripes, meshes, waves, circles and lattices.
  • a material chemically stable with respect to the lithium metal may be used.
  • Specific examples thereof include polymer films such as polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polyimide and polyamide, and polyethylene terephthalate Phthalate is preferable from the viewpoint of releasability.
  • the thickness of the lithium metal applied to the cathode is preferably 2 to 200 ⁇ ⁇ , more preferably 3 to 40 ⁇ ⁇ , and most preferably 5 to 20 ⁇ ⁇ .
  • the thickness of the lithium metal is less than 2 ⁇ , it is not preferable from the viewpoint of total lithization, and when the thickness of the lithium metal is more than 200 ⁇ , there is a risk of short circuit.
  • the lithium metal sheet refers to a lithium metal coated or adhered onto a release film.
  • the thickness of the release film is 5 to 50 mu m, more preferably 10 to 40 mu m, and most preferably 15 to 30 mu m. If the thickness of the release film is too thin, it is difficult to peel off the release film. If the thickness of the release film is too thick, lithium metal may be desorbed together with peeling off the release film.
  • a method for producing a cathode coated with lithium metal can be carried out by placing a rolled lithium metal sheet on a negative electrode mixture layer and passing the negative electrode laminated with lithium metal through a pair of rollers or plates.
  • the temperature at the time of passing through the roller or the plate is preferably 5 to 100 ⁇ ⁇ , more preferably 15 to 30 ⁇ ⁇ , and most preferably 20 to 25 ⁇ ⁇ . If the temperature is too low, a part of the lithium metal may be desorbed from the cathode. If the temperature is too high, the handling of the lithium metal may be deteriorated.
  • the pressure applied when the negative electrode having the lithium metal laminated on the roller or the plate is passed is 10 to 100 kg / cm 2, preferably 20 to 100 kg / cm 2, and most preferably 30 to 100 kg / cm 2. If the applied pressure is too low, it is difficult to achieve the object of the present invention, and if it is too high, the electrode may break.
  • the secondary battery according to the present invention comprises an electrode assembly in which two electrodes of different polarities are laminated in a state separated from each other by a separator.
  • the electrode assembly includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, And a separation membrane.
  • the anode is prepared, for example, by coating a mixture of a cathode active material, a conductive material and a binder on a cathode current collector, followed by drying, and if necessary, further adding a filler to the mixture.
  • the cathode active material according to the present invention is a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; A lithium manganese oxide (LiMnO 2 ) such as LiMnO 3 , LiMn 2 O 3 , LiMnO 2, etc.
  • the cathode current collector generally has a thickness of 3 to 500 mu m.
  • a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, and may be formed of a material such as stainless steel, aluminum, nickel, titanium, sintered carbon, or a surface of aluminum or stainless steel Treated with carbon, nickel, titanium, silver or the like may be used.
  • the current collector may have fine irregularities on the surface thereof to increase the adhesive force of the cathode active material, and various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric are possible.
  • the conductive material is usually added in an amount of 1 to 50% by weight based on the total weight of the mixture including the cathode active material.
  • a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the binder is a component that assists in bonding of the active material and the conductive material and bonding to the current collector, and is usually added in an amount of 1 to 50 wt% based on the total weight of the mixture containing the cathode active material.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
  • the filler is optionally used as a component for suppressing the expansion of the anode, and is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery.
  • the filler include olefin polymers such as polyethylene and polypropylene; Fibrous materials such as glass fibers and carbon fibers are used.
  • the negative electrode is manufactured by applying a negative electrode material on a negative electrode collector and drying the same, and may further include the above-described components as needed.
  • the negative electrode collector is generally made to have a thickness of 3 to 500 mu m.
  • Such an anode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, and may be formed of a material such as copper, stainless steel, aluminum, nickel, titanium, fired carbon, surface of copper or stainless steel A surface treated with carbon, nickel, titanium, silver or the like, an aluminum-cadmium alloy, or the like can be used.
  • fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as films, sheets, foils, nets, porous bodies, foams and nonwoven fabrics.
  • the negative electrode active material of the present invention is not particularly limited as long as it is a material capable of reversibly storing / releasing lithium ions such as silicon (Si) and tin. Particularly, in the case of a silicon (Si) based active material, the volume change and the surface side reaction are so severe that a large amount of lithium inserted into the negative electrode at the time of initial charging can not return to the positive electrode again, So that the effect of the present invention is further maximized.
  • any of the above materials can exert the effects of the present invention even if it is a composite, an alloy, a compound, a solid solution, and a composite negative active material containing a silicon-containing material or a tin-containing material.
  • a silicon containing material, Si, SiO x (0 ⁇ x ⁇ 4) , or in any one of these B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, V, W, Zn, C, N, and Sn, or a compound or solid solution thereof may be used.
  • These materials may constitute the negative active material alone or may constitute the negative active material by a plurality of kinds of materials.
  • Examples of constituting the negative electrode active material by the above-mentioned plural kinds of materials include a compound containing Si, oxygen and nitrogen, a composite of a plurality of compounds containing Si and oxygen and having different composition ratios of Si and oxygen, and the like .
  • a polyolefin-based separator commonly known as a separator for insulating the electrodes between the anode and the cathode or a composite separator having an organic-inorganic composite layer formed on the olefin-based substrate may be used without particular limitation.
  • the electrolyte solution injected into the secondary battery is a lithium salt-containing non-aqueous electrolyte, which is composed of a non-aqueous electrolyte and lithium.
  • a non-aqueous electrolyte a non-aqueous electrolyte, a solid electrolyte, an inorganic solid electrolyte and the like are used.
  • nonaqueous electrolytic solution examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, But are not limited to, lactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, Nitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives , Tetrahydrofuran derivatives, ether, methyl pyrophosphate, ethyl propionate and the like can be used.
  • organic solid electrolyte examples include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, Polymers containing ionic dissociation groups, and the like can be used.
  • a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, Polymers containing ionic dissociation groups, and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides and sulfates of Li such as Li 4 SiO 4 -LiI-LiOH and Li 3 PO 4 -Li 2 S-SiS 2 can be used.
  • non-aqueous electrolytes may be used in the form of, for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, glyme, N, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride and the like are added It is possible.
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further added to impart nonflammability, or a carbon dioxide gas may be further added to improve high-temperature storage characteristics.
  • a method of manufacturing an electrode assembly comprising: preparing an electrode assembly having a separator interposed between a cathode and an anode; Injecting an electrolyte solution into the electrode assembly; And aging the battery, wherein initial charging is initiated by injecting an electrolyte solution. At this time, aging is preferably performed for 12 to 72 hours, more preferably for 24 to 48 hours.
  • the secondary battery including the negative electrode for a secondary battery of the present invention is characterized in that charging is started as lithium ions are stored in the negative electrode immediately after the electrolyte solution is injected into the secondary battery even if artificially initial charging is not performed after the electrode assembly is manufactured.
  • a negative electrode mixture slurry was prepared by adding 92 wt% of SiO 2, 3 wt% of denka black (conductive agent), 3.5 wt% of SBR (binder), and 1.5 wt% of CMC (thickener) as an anode active material to water.
  • the anode mixture slurry was coated on one surface of the copper collector, dried and rolled, and then punched to a predetermined size to prepare an anode mixture.
  • a lithium metal sheet laminated with a lithium metal having a thickness of 10 mu m on a silicon (PET) (polyethylene terephthalate) substrate having a thickness of 20 mu m and wound in a roll form was prepared.
  • a lithium metal sheet prepared in the prepared negative electrode material mixture was laminated, and a pressure of 15 kg / cm 2 was applied while passing through a pair of rollers having a temperature of 25 ⁇ to prepare a lithium metal-coated negative electrode.
  • the prepared positive electrode mixture slurry was coated on one surface of the aluminum current collector to a thickness of 100 ⁇ , dried and rolled, and punched to a predetermined size to prepare a positive electrode material mixture.
  • a coin cell having a polypropylene porous film interposed between the prepared positive electrode mix and negative electrode mix was prepared.
  • a lithium secondary battery was prepared by injecting an electrolyte in which 1 M lithium hexafluorophosphate (LiPF 6 ) was dissolved in a solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (DEC) were mixed at a volume ratio of 50:50.
  • LiPF 6 lithium hexafluorophosphate
  • EC ethylene carbonate
  • DEC ethyl methyl carbonate
  • a secondary battery was produced under the same conditions as in Example 1 except that a lithium metal having a pattern formed in a mesh form was used. At this time, the size of the pattern is 0.1 ⁇ * 0.1 ⁇ .
  • a secondary battery was produced under the same conditions as in Example 2, except that the thickness of the lithium metal was changed to 20 mu m.
  • a secondary battery was manufactured under the same conditions as in Example 2, except that the pressure applied by the roller was changed to 30 kg / cm 2.
  • a secondary battery was manufactured under the same conditions as in Example 1 except that a lithium metal laminate in which lithium metal was laminated on a PET substrate not coated with silicon was bonded to the negative electrode mixture.
  • a secondary battery was produced under the same conditions as in Example 1, except that the temperature of the roller was changed to 120 ⁇ .
  • a secondary battery was produced under the same conditions as in Example 1, except that the pressure applied by the roller was changed to 120 kg / cm 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une anode de batterie secondaire, et l'anode, le procédé comprenant : une première étape consistant à préparer une feuille de lithium métal, comportant un lithium métal sous forme de film mince revêtant ou étant fixé à un film de libération, et étant enroulée en un rouleau ; une deuxième étape consistant à fabriquer une anode sur laquelle est empilé le lithium métal, par un empilement de la feuille de lithium métal de sorte que le lithium métal soit adjacent à un mélange d'anode ; et une troisième étape consistant à fabriquer une anode par une application d'une pression à l'anode sur laquelle est empilé le lithium métal, le film de libération étant revêtu de silicium. Le procédé de fabrication d'une anode, selon la présente invention, a pour effet d'empiler ou d'assembler uniformément un lithium métal, qui est difficile à manipuler, sur le mélange d'anode d'une batterie secondaire, et offre l'avantage d'améliorer un taux de pré-lithiation au moyen d'un lithium métal ayant un motif.
PCT/KR2018/007789 2017-07-31 2018-07-10 Procédé de fabrication d'anode de batterie secondaire et anode de batterie secondaire Ceased WO2019027152A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202311538900.7A CN117691050A (zh) 2017-07-31 2018-07-10 二次电池用负极的制造方法和二次电池用负极
CN201880003741.1A CN109792046A (zh) 2017-07-31 2018-07-10 二次电池用负极的制造方法和二次电池用负极
EP18841091.4A EP3503266A4 (fr) 2017-07-31 2018-07-10 Procédé de fabrication d'anode de batterie secondaire et anode de batterie secondaire
US16/376,439 US11658285B2 (en) 2017-07-31 2019-04-05 Method for manufacturing negative electrode for secondary battery and negative electrode for secondary battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2017-0096794 2017-07-31
KR1020170096794A KR102283684B1 (ko) 2017-07-31 2017-07-31 이차전지용 음극의 제조방법 및 이차전지용 음극

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/376,439 Continuation US11658285B2 (en) 2017-07-31 2019-04-05 Method for manufacturing negative electrode for secondary battery and negative electrode for secondary battery

Publications (1)

Publication Number Publication Date
WO2019027152A1 true WO2019027152A1 (fr) 2019-02-07

Family

ID=65234077

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/007789 Ceased WO2019027152A1 (fr) 2017-07-31 2018-07-10 Procédé de fabrication d'anode de batterie secondaire et anode de batterie secondaire

Country Status (5)

Country Link
US (1) US11658285B2 (fr)
EP (1) EP3503266A4 (fr)
KR (1) KR102283684B1 (fr)
CN (2) CN117691050A (fr)
WO (1) WO2019027152A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111261836A (zh) * 2019-12-23 2020-06-09 中国科学院宁波材料技术与工程研究所 锂离子电池负极预锂化的方法和经过预锂化的锂离子电池的制备方法

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102859318B1 (ko) * 2019-07-08 2025-09-11 주식회사 엘지에너지솔루션 음극의 제조방법
KR102658723B1 (ko) * 2019-09-06 2024-04-19 주식회사 엘지에너지솔루션 리튬 이차전지용 음극의 제조방법
CN111244555A (zh) * 2019-10-10 2020-06-05 江苏正力新能电池技术有限公司 一种高比例硅负极固相补锂工艺
US20210184199A1 (en) * 2019-12-11 2021-06-17 GM Global Technology Operations LLC Methods of lithiating metal anodes using electrolytes
GB202000467D0 (en) * 2020-01-13 2020-02-26 Sigma Lithium Ltd Alkali metal materials
KR102846665B1 (ko) * 2020-03-27 2025-08-18 주식회사 엘지에너지솔루션 음극의 제조방법
KR102876036B1 (ko) 2020-07-01 2025-10-23 주식회사 엘지에너지솔루션 리튬-황 전지용 양극 및 이의 제조방법
KR20220051500A (ko) 2020-10-19 2022-04-26 주식회사 엘지에너지솔루션 무기 코팅층이 형성된 음극의 제조방법
KR20220059279A (ko) * 2020-11-02 2022-05-10 주식회사 엘지에너지솔루션 전리튬화층을 포함하는 리튬 금속 전지용 음극, 이의 제조방법, 및 이를 포함하는 리튬 금속 전지
KR102378979B1 (ko) 2021-07-26 2022-03-25 (주)미디어테크 리튬메탈 배터리용 인라인 제조장치
CN113437280B (zh) * 2021-08-30 2021-11-30 北京壹金新能源科技有限公司 一种浆料稳定的锂化硅基复合材料及其制备方法和应用
KR20230118514A (ko) * 2022-02-04 2023-08-11 주식회사 엘지에너지솔루션 리튬 이차 전지용 음극의 제조 방법, 리튬 이차 전지용 음극 및 음극을 포함하는 리튬 이차 전지
KR102830047B1 (ko) * 2022-02-09 2025-07-03 주식회사 엘지에너지솔루션 리튬 이차 전지용 음극의 전리튬화 방법, 음극 중간체 및 음극을 포함하는 리튬 이차 전지
KR20230156661A (ko) * 2022-05-06 2023-11-14 주식회사 엘지에너지솔루션 전극 조립체의 제조 방법, 전극 조립체 및 이를 포함하는 리튬 이차 전지
EP4418354A4 (fr) * 2022-05-19 2025-11-12 Lg Energy Solution Ltd Procédé de fabrication d'électrode pour batterie secondaire au lithium, et batterie secondaire au lithium comprenant une électrode
WO2024101938A1 (fr) * 2022-11-10 2024-05-16 주식회사 엘지에너지솔루션 Batterie tout solide et son procédé de fabrication
KR20250002968A (ko) * 2023-06-30 2025-01-07 주식회사 엘지에너지솔루션 리튬 금속 타발용 필름 및 이를 이용한 리튬 금속의 타발 방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06140028A (ja) * 1992-10-28 1994-05-20 Yuasa Corp 負極集電体及びその製造方法
JPH10289708A (ja) * 1997-04-11 1998-10-27 Japan Storage Battery Co Ltd 非水電解質二次電池及びその電極板の製造方法
KR20050007484A (ko) * 2003-07-08 2005-01-19 삼성에스디아이 주식회사 리튬 이차 전지용 음극, 그의 제조 방법 및 그를 포함하는리튬 이차 전지
JP2013020974A (ja) * 2006-03-09 2013-01-31 Panasonic Corp 転写用フィルムの製造方法、および電気化学素子用の極板の製造方法
JP2016146232A (ja) * 2013-05-30 2016-08-12 三洋電機株式会社 電池用リチウム薄膜積層体

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4502903A (en) 1982-01-20 1985-03-05 Polaroid Corporation Method of making lithium batteries with laminar anodes
US4622277A (en) 1985-09-30 1986-11-11 Duracell Inc. Electrochemical cells
US5435054A (en) 1993-11-15 1995-07-25 Valence Technology, Inc. Method for producing electrochemical cell
US6406817B2 (en) * 1998-07-01 2002-06-18 Ube Industries, Ltd. Crosslinked polymer, electrolyte using the polymer, and nonaqueous secondary battery using the electrolyte
US6761744B1 (en) 1999-07-16 2004-07-13 Quallion Llc Lithium thin film lamination technology on electrode to increase battery capacity
US20050130043A1 (en) 2003-07-29 2005-06-16 Yuan Gao Lithium metal dispersion in electrodes
JP4920880B2 (ja) * 2003-09-26 2012-04-18 三星エスディアイ株式会社 リチウムイオン二次電池
KR20060020904A (ko) 2004-09-01 2006-03-07 브이케이 주식회사 적층형 리튬 이차 전지 및 그 제조방법
JP4502903B2 (ja) 2005-08-01 2010-07-14 中野製薬株式会社 ２剤式酸化染毛・脱色剤組成物
US7754390B2 (en) 2006-03-14 2010-07-13 Panasonic Corporation Manufacturing method of negative electrode for nonaqueous electrolytic rechargeable battery, and nonaqueous electrolytic rechargeable battery using it
KR100824048B1 (ko) * 2006-11-01 2008-04-22 고려대학교 산학협력단 리튬 전지용 음극, 그 제조방법 및 이를 채용한 리튬 전지
US9401525B2 (en) 2009-03-20 2016-07-26 Semiconductor Energy Laboratory Co., Ltd. Power storage device and manufacturing method thereof
KR101106359B1 (ko) * 2009-09-25 2012-01-18 삼성에스디아이 주식회사 리튬 이온 이차 전지 제조 방법
WO2011085174A2 (fr) * 2010-01-07 2011-07-14 Hid Global Corporation Laminage à transfert
CN202121011U (zh) * 2011-06-03 2012-01-18 武汉市弘阳科技发展有限公司 金属锂复合结构锂离子电池负极
JP5949914B2 (ja) * 2012-05-21 2016-07-13 ダイキン工業株式会社 電極合剤
CN103199217B (zh) 2013-04-02 2015-06-03 东莞新能源科技有限公司 锂离子电池的富锂极片及其制备方法
JP2015007283A (ja) 2013-05-30 2015-01-15 パナソニックＩｐマネジメント株式会社 薄膜製造装置及び薄膜製造方法、並びに、電気化学デバイス及び電気化学デバイスの製造方法
KR101820463B1 (ko) 2013-07-30 2018-01-19 주식회사 엘지화학 음극 전극의 전리튬화 방법
KR102155696B1 (ko) * 2013-09-13 2020-09-15 삼성전자주식회사 복합막, 그 제조방법 및 이를 포함한 리튬 공기 전지
CN105374571B (zh) 2014-08-26 2018-01-23 万星光电子(东莞)有限公司 锂离子电容器负极片及其制备方法、卷绕型锂离子电容器
CN104577086B (zh) 2014-12-17 2017-01-04 李震祺 一种预锂化和石墨烯包覆的介孔SiO负极材料及其制备方法
US10476065B2 (en) * 2015-01-09 2019-11-12 Applied Materials, Inc. Lithium metal coating on battery separators
KR101772419B1 (ko) 2015-03-02 2017-09-12 주식회사 엘지화학 분리막과 접착력이 향상된 이차전지용 전극
CN105489846B (zh) * 2016-01-11 2018-03-20 宁德时代新能源科技股份有限公司 极片补锂方法及系统
KR20180100706A (ko) * 2016-01-28 2018-09-11 어플라이드 머티어리얼스, 인코포레이티드 보호 층 툴을 갖는 통합형 리튬 증착
US10755867B2 (en) 2016-04-18 2020-08-25 Florida State University Research Foundation, Inc Method of negative electrode pre-lithiation for lithium-ion capacitors
CN106450467A (zh) * 2016-09-07 2017-02-22 中南大学 一种储能器件的补锂方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06140028A (ja) * 1992-10-28 1994-05-20 Yuasa Corp 負極集電体及びその製造方法
JPH10289708A (ja) * 1997-04-11 1998-10-27 Japan Storage Battery Co Ltd 非水電解質二次電池及びその電極板の製造方法
KR20050007484A (ko) * 2003-07-08 2005-01-19 삼성에스디아이 주식회사 리튬 이차 전지용 음극, 그의 제조 방법 및 그를 포함하는리튬 이차 전지
JP2013020974A (ja) * 2006-03-09 2013-01-31 Panasonic Corp 転写用フィルムの製造方法、および電気化学素子用の極板の製造方法
JP2016146232A (ja) * 2013-05-30 2016-08-12 三洋電機株式会社 電池用リチウム薄膜積層体

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3503266A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111261836A (zh) * 2019-12-23 2020-06-09 中国科学院宁波材料技术与工程研究所 锂离子电池负极预锂化的方法和经过预锂化的锂离子电池的制备方法

Also Published As

Publication number Publication date
KR102283684B1 (ko) 2021-08-02
CN117691050A (zh) 2024-03-12
US20190237750A1 (en) 2019-08-01
US11658285B2 (en) 2023-05-23
EP3503266A4 (fr) 2019-10-23
EP3503266A1 (fr) 2019-06-26
CN109792046A (zh) 2019-05-21
KR20190012973A (ko) 2019-02-11

Similar Documents

Publication Publication Date Title
WO2019027152A1 (fr) Procédé de fabrication d'anode de batterie secondaire et anode de batterie secondaire
KR102261504B1 (ko) 이차전지용 음극의 전리튬화 방법
WO2020055183A1 (fr) Anode pour batterie secondaire au lithium et procédé de fabrication de batterie secondaire au lithium
WO2019031732A1 (fr) Pré-lithiation utilisant une couche composite de métal lithium et de matériau inorganique
WO2018212453A1 (fr) Procédé de pré-lithiation d'anode d'oxyde de silicium destinée à une batterie secondaire
KR101463996B1 (ko) 안전성이 향상된 리튬 이차 전지
WO2020159236A1 (fr) Procédé de pré-lithiation d'électrode négative pour batterie secondaire
KR20190017651A (ko) 리튬금속과 무기물 복합박막 제조방법 및 이를 이용한 리튬 이차전지 음극의 전리튬화 방법
WO2015102140A1 (fr) Anode pour batterie rechargeable, et batterie rechargeable au lithium comprenant cette dernière
WO2015102139A1 (fr) Électrode négative pour batterie secondaire et batterie secondaire au lithium comprenant celle-ci
WO2019147082A1 (fr) Anode pour batterie secondaire au lithium et batterie secondaire au lithium-ion comprenant l'anode
WO2020071814A1 (fr) Anode à structure multicouche comprenant un composé à base de silicium, et batterie secondaire au lithium la comprenant
WO2022244918A1 (fr) Anode ayant une structure multicouche et batterie secondaire la comprenant
US12347853B2 (en) Method for manufacturing negative electrode for lithium secondary battery
WO2018048126A1 (fr) Procédé de fabrication d'électrodes de qualité uniforme et procédé de fabrication d'un ensemble d'électrodes comprenant lesdites électrodes
WO2020251165A1 (fr) Procédé de fabrication de batterie secondaire au lithium comprenant une étape de traitement thermique supplémentaire et batterie secondaire au lithium fabriquée par ce moyen
WO2019221410A1 (fr) Électrode négative comprenant une couche de protection d'électrode et batterie secondaire au lithium l'utilisant
US11043663B2 (en) Method for manufacturing high-loading electrode
WO2021020853A1 (fr) Ensemble électrode de type roulé comprenant une anode dans laquelle des mélanges d'anodes comprenant des matériaux actifs de différentes compositions sont formés sur les deux surfaces d'un collecteur de courant, batterie secondaire comprenant celui-ci, et dispositif comprenant une batterie secondaire
WO2019017617A1 (fr) Électrode n'ayant pas de collecteur de courant et accumulateur la comprenant
WO2022085995A1 (fr) Procédé de fabrication d'anode comportant une couche de revêtement inorganique formée sur cette dernière
WO2021167353A1 (fr) Procédé de pré-lithiation d'électrode négative, électrode négative pré-lithiée et batterie secondaire au lithium la comprenant
WO2018147558A1 (fr) Procédé de fabrication d'électrode pour batterie secondaire appropriée pour une longue durée de vie
WO2021225416A1 (fr) Collecteur de courant d'électrode négative pour batterie sans lithium, ensemble électrode comprenant celui-ci et batterie sans lithium
WO2020111746A1 (fr) Procédé de fabrication de batterie secondaire au lithium

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18841091

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018841091

Country of ref document: EP

Effective date: 20190320

NENP Non-entry into the national phase

Ref country code: DE